The subject matter of the invention includes cosmetic compositions containing at least one inorganic-organic hybrid prepolymer and methods of treating hair, skin or nails using inorganic-organic hybrid prepolymers or crosslinked inorganic-organic hybrid polymers.
People have always considered an attractive external appearance to be important. The hair-do plays a special role in this respect. The basis for an attractive external appearance is well-groomed and well cared-for hair. There are many known products which by means of added polymers confer to hair good hold, volume, elasticity, springiness and sheen. These styling products, for example in the form of gels, facilitate shaping, as sprays they improve the firmness and as foaming fixatives they improve the hair volume. Moreover, besides good hold, natural springiness and elasticity, styling products confer to hair a natural sheen.
Hair fixatives and hair-care agents usually consist of solutions of film-forming synthetic or natural polymers. Suitable synthetic polymers are, for example, polyvinylpyrrolidone, polyvinylpyrrolidone-polyvinyl acetate copolymers and polyacrylic or polymethacrylic acid polymers. Useful natural polymers include, for example, shellac, gelatin, chitosan salts, polysaccharides and derivatives thereof and cellulose derivatives.
In terms of hair-conditioning and particularly hair-setting properties, however, not all the aforesaid substances are as yet fully satisfactory. Their drawbacks manifest themselves, for example, in that it is very difficult to meet all or several of the desired requirements at the same time and that conventional polymers are washed out of the hair after only one washing. As a result, the volume and hair-do disappear completely, and a new hair-do is required.
Hence, a need exists to further improve the hold, elasticity, springiness, feel and sheen of human hair. According to the invention, this objective can be reached by use of inorganic-organic hybrid prepolymers which after being applied to the hair are crosslinked to form inorganic-organic hybrid polymers.
We have found that inorganic-organic hybrid prepolymers can also be used in cosmetic agents and that marked improvement can be achieved in agents intended to produce longer-lasting hair-dos and hair grooming if they contain at least one inorganic-organic hybrid prepolymer. By crosslinking the prepolymers on the hair, the resulting polymers are more strongly linked with the hair and, hence, can better stabilize the hair-do. By an appropriate choice of the polymers, it is also possible to confer to the hair a good feel and sheen besides good hold.
The inorganic-organic hybrid polymers formed by the crosslinking of the prepolymers in accordance with the invention are also known under the name ORMOCER(copyright) (organic modified ceramics). These are silicone polymers occupying a special place between the classical glasses defined as inorganic glasses (silicates) and crosslinked organic polymers. The hybrid polymers can be prepared by a method known as the sol-gel process and they are known as coating materials for metals, glass, stone, polymers etc (Fraunhofer-Institut fxc3xcr Silicatforschung [Fraunhofer Institute for Silicate Research] (ISC), Progress Report, pages 51 to 60 and literature references cited therein). Other reviews concerning the preparation, use and properties of inorganic-organic hybrid polymers can be found in xe2x80x9cSintesis y preparacion de materiales hibridos organico/inorganico. Ormoceros. Nuevas aplicaciones de los materiales polimerosxe2x80x9d; [Synthesis and Preparation of Organic/inorganic Hybrid Materials. Ormocers. New Applications of Polymeric Materials], Revista de Plasticos No.483, September 1996, pp.257-274, and literature references cited therein, as well as in xe2x80x9cORMOCERxe2x80x9d: Neuer Korrosionsschutz fxc3xcr Messingoberflxc3xa4chenxe2x80x9d [ORMOCER: A New Corrosion Inhibitor for Brass Surfaces], Jahrbuch Oberflxc3xa4chentechnik (1993), 49, pp. 243-251.
Processes for the preparation of inorganic-organic hybrid polymers and prepolymers and their use as coating materials for, among other things, metal surfaces or fabrics made of natural fibers are described, for example, in German Unexamined Patent Application DE-OS 38 28 098, EP 0 526 875, EP 0 580 488, EP 0 610 831, EP 0 792 846 and WO 95/13855.
The synthesis of hybrid prepolymers is based on the use of functionalized silanes having general formula (I)
RSiX3xe2x80x83xe2x80x83(I) 
wherein X denotes a hydrolyzable and condensable group and R stands for a crosslinkable organic group. First, hydrolytic precondensation affords the inorganic Sixe2x80x94Oxe2x80x94Si network which is then crosslinked further by reactions of the crosslinkable organic R groups.
By hybrid prepolymers in the sense of the present invention are meant products obtained by precondensation and which are not yet crosslinked through the R groups.
The crosslinkable R group usually denotes an aliphatic side group which can contain various functional groups, such as amino, epoxy, hydroxyl, methacrylate or other polymerizable groups. In particular, R can be selected from among alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl or alkynylaryl groups. The R group can be interrupted by O, S or N atoms and, if it is not in itself polymerizable, contains at least one crosslinkable substituent from the group consisting of halogens, amino, amido, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy, methacryloxy, epoxy or vinyl groups.
The X groups can denote, independently of each other, alkoxy, aryloxy, acyloxy, alkylcarbonyl or alkoxycarbonyl groups, halogen, hydrogen or a substituted or unsubstituted amino group. Ethoxy and methoxy groups are particularly preferred.
In particular, the silane of formula (I) can be selected from among vinyltrialkoxysilanes, vinyltriacetoxysilanes, aminopropyltrialkoxysilanes, isocyanatopropylalkoxysilanes, mercaptopropyltrialkoxysilanes, vinyltrichlorosilane, allyltrialkoxysilanes, allyltriacetoxysilane, 3-isocyanatooxypropyltrialkoxysilanes, methacryloxypropenyltrialkoxysilanes, 3-methacrylocarbonyloxypropyltrialkoxysilanes, 3-cyanopropyltrialkoxysilanes, 4-mercaptobutyltrialkoxysilanes, 6-mercaptohexyltrialkoxysilanes, 3-mercaptopropyltrialkoxysilanes, 3-(ethylenediamino)propyltrialkoxysilanes, 3-(diethylenetriamino)propylalkoxysilanes, 3-glycidoxypropyltrialkoxysilanes, 2-[4-(1,2-epoxycyclohexyl)]ethyltrialkoxysilanes and 3-(trialkoxysilyl)propylsuccinic anhydride, wherein the alkoxy groups denote methoxy or ethoxy groups. 3-Glycidoxypropyltrialkoxysilanes and 3-mercaptopropyltrialkoxysilanes are particularly preferred.
Precondensed silane oligomers soluble in the reaction mixture can be used in place of the monomeric starting silanes. Fluorinated silane derivatives can also be used.
The compounds of general formula (I) can be combined with metal compounds, for example with the alkyl, alkoxy, halogen, acyloxy, hydroxy, oxyhalogen or hydroxyhalogen compounds of titanium, zirconium or aluminum as well as with other network-modifying compounds, for example those of formula SiX4 (II) or compounds of formula SiRxe2x80x2X2R (III), wherein Rxe2x80x2 denotes a non-crosslinkable, non-condensable alkyl or aryl group, and R and X have the afore-indicated meaning.
The network-modifying compounds, for example in the case of compounds of formula (II), can bring about an increase or, in the case of compounds of type (III) a decrease, in the degree of crosslinking in the inorganic part.
In particular, the metal compounds of the transition metals, particularly those of subgroup IV, preferably Ti or Zr compounds, or of main groups III or IV, preferably aluminum compounds, can be selected from among titanium tetrachloride, tetraalkoxytitanium, zirconium tetrachloride, tetraalkoxyzirconium, dichlorozirconium oxide, trialkoxyaluminum, dihydroxyaluminum chloride, tributoxyaluminum and tetrapropoxyzirconium, wherein alkoxy stands for methoxy, ethoxy, isopropoxy, n-propoxy, butoxy or 2-ethylhexoxy.
In particular, the compound of formula (II) can be selected from among tetramethoxysilane, tetraethoxysilane, trimethoxysilane, tetra-n-propoxysilane or tetraisopropoxysilane, tetrabutoxysilane, tetrachlorosilane, trichlorosilane and tetraacetoxysilane.
Other network-modifying compounds can be selected from among methyltrichlorosilane, methyltrialkoxysilanes, ethyltrichlorosilane, ethyltrialkoxysilanes, propyltrialkoxysilanes, phenyltrialkoxysilanes, dimethyldichlorosilane, dimethyldialkoxysilanes, dimethyldihydrosilane, diphenyldichlorosilane, diphenyldialkoxysilanes, tripropylhydroxysilane, 4-aminobutylmethyidialkoxysilanes, aminomethyldimethylalkoxysilanes, vinylethyidichlorosilane, vinylmethyldiacetoxysilane, vinylmethyidichlorosilane, vinylmethyldialkoxysilanes, phenylvinyldialkoxysilanes, phenylvinyldialkoxysilanes, phenylallyidichlorosilane, 4-aminobutylmethyidialkoxysilanes, aminomethyidimethylalkoxysilanes and comparable compounds, wherein the alkoxy groups are preferably methoxy or ethoxy groups.
The preparation and the use of inorganic-organic hybrid polymers involves hydrolysis of the starting compounds to form a colloidal solution which contains the cleaved-off hydrolysis products, for example the alcohols, and which is also referred to as the coating material. This coating material is either applied directly to the substrate (for example to the hair, skin or nails) or it can be incorporated into conventional cosmetic agents. In a second step, following the formation of the inorganic Sixe2x80x94Oxe2x80x94Si network, the organic molecular groups are crosslinked with each other. This can be accomplished by conventional polymerization reactions, for example by reactions involving double bonds. Polyaddition reactions, such as those occurring with epoxy resins, can also be used to crosslink organic side chains.
Preferably, the precondensation is carried out in the presence of a condensation catalyst. Suitable condensation catalysts are proton- and hydroxyl ions-eliminating compounds and amines. German Unexamined Patent Application DE-OS 38 28 098 deals with a process based on precondensation. The present invention includes the condensation catalysts mentioned in that application.
The inorganic-organic hybrid prepolymers can be used for hair treatment by subjecting, in a first step, at least one organofunctional silane of formula (I) to hydrolytic precondensation, optionally in the presence of at least one condensation catalyst, and then, in a second step, crosslinking it to form the hybrid polymer. Crosslinking can be induced by the action of heat, light or a suitable polymerization catalyst and is preferably carried out after the material has been applied to the hair.
Hybrid prepolymers in the form of an inorganic network (precondensation product of the first reaction step) can be incorporated into aqueous, alcoholic or aqueous/alcoholic hair-setting and hair-care agents and thus applied to the hair. By exposure to heat, the organic network is then formed on the hair thus setting the hair-do. Depending on the properties of this polysiloxane, a more stable or better-groomed hair with a pleasant, natural feel and considerable sheen is obtained.
Preferred systems for the formation of inorganic-organic hybrid polymers are the following:
1) 3-glycidoxypropyltrimethoxysilane, 3-triethoxysilylpropylsuccinic anhydride and 1-methylimidazole, preferably in a weight proportion of 45-65:30-45:1, for example 57.4:36.9:1;
2) 3-glycidoxypropyltrimethoxysilane, trimethoxyphenylsilane and aminosilane, for example aminopropyltriethoxysilane, tributoxyaluminum and ethyl acetoacetate, preferably in a weight proportion of 1-2:1.5-2.5:1:4-5:2-3, for example 1.4:1.8:1:4.45:2.75.
3) 3-glycidoxypropyltrimethoxysilane, tetramethoxysilane, tributoxyaluminum, tetrapropoxyzirconium and triethanolamine, preferably in a weight proportion of 4.5-5.5:2-3:0.8-1.8:1.7-2.5:1, for example 5.1:2.5:1.2:2.1:1;
4) 3-glycidoxypropyltrimethoxysilane, trimethoxyphenylsilane, 2,2,2-trifluoroethylamine, tributoxyaluminum and ethyl acetoacetate, preferably in a weight proportion of 13-16:1.5-2.5:1:3-5:2-3.5, for example 14.4:1.9:1:4.0:2.6;
5) 3-methacryloxypropyltrimethoxysilane and tetrapropoxyzirconium, preferably in a weight ratio of 2-3.5:1, for example 2.6:1, with a UV or thermal initiator;
6) 3-glycidoxypropyltrimethoxysilane, trimethoxyphenylsilane, aminosilane, for example aminopropyltriethoxysilane, tributoxyaluminum and ethyl acetoacetate, preferably in a weight proportion of 6-9:1:0.8-1.5:2-3:1-2, for example 7.2:1:1.1:2.5:1.3;
7) 3-glycidoxypropyltrimethoxysilane, trimethoxyphenylsilane, aminosilane, for example aminopropyltriethoxysilane, tributoxyaluminum and tetrapropoxyzirconium, preferably in a weight proportion of 9-10.4:3.8-4.5:1:0.8-2.8:3-5, for example 9.6:4.1:1:2.2:3.9;
8) 3-glycidoxypropyltrimethoxysilane, aminosilane, for example aminopropyltriethoxysilane and 3-mercaptotriethoxysilane, preferably in a weight proportion of 18-21:1:6.5-8, for example 19.2:1:7.2;
9) mercaptopropyltriethoxysilane and hydrochloric acid (1 N) in a molar ratio of, preferably, 1:1-2, for example 1:1.5;
10) 3-glycidoxypropyltrimethoxysilane, trimethoxyphenylsilane, tributoxyaluminum and ethyl acetoacetate, preferably in a weight proportion of 5-6:1-2:1-2.5:1, for example 5.4:1.5:1.9:1.
11) mercaptopropyltriethoxysilane and vinyltriethoxysilane, preferably in a weight ratio of 1-2:1, for example 1.25:1, and aqueous hydrochloric acid (1 N).
Systems 3), 9) and 11) are particularly preferred.
Advantageously, the inorganic-organic hybrid polymer or prepolymer can also be used as a carrier for active or auxiliary cosmetic or pharmaceutical ingredients, for example antidandruff products, dyes or pigments. To this end, the active or auxiliary ingredients can be either physically incorporated or chemically bound.
Another object of the invention is a process for hair treatment whereby
a) a not-as-yet-crosslinked precondensation product of an inorganic-organic hybrid polymer in an appropriate cosmetic base is applied to the hair and
b) subsequently crosslinked to form the hybrid polymer.
To this end, the crosslinking can be induced by heat, light or a polymerization initiator. Suitable initiators are, for example, 1-hydroxycyclohexyl phenyl ketone or tert.butylperoxy 2-ethylhexanoate. Thermally induced crosslinking is carried out at 20 to 80xc2x0 C., preferably at 40 to 50xc2x0 C. and particularly at 40 to 50xc2x0 C., preferably for 2 to 20 minutes.
Yet another object of the present invention are cosmetic agents containing at least one inorganic-organic hybrid prepolymer in an appropriate cosmetic base. In a cosmetic agent according to the invention, the hybrid prepolymer is contained in an amount from, preferably, 0.01 to 40 wt % and particularly in an amount from 0.05 to 15 wt %, in an appropriate cosmetic base.
In general, the agent according to the invention is used as an aqueous, alcoholic or aqueous-alcoholic solution. Suitable solvents are, for example, aliphatic alcohols with 1 to 4 carbon atoms or a mixture of water and one of said alcohols. Other organic solvents can also be used, among them, in particular, unbranched or branched hydrocarbons, such as pentane, hexane, isopentane and cyclic hydrocarbons such as cyclopentane and cyclohexane. The solvent is used in an amount from 0.5 to 99 wt % and preferably from 40 to 90 wt %.
In a particular embodiment of the invention, the inorganic-organic hybrid prepolymer is used together with at least one film-forming and hair-setting polymer. The film-forming and hair-setting polymer can be of synthetic or natural origin and have a nonionic, cationic, anionic or amphoteric character. Such an added polymer which in the hair-treating agent is present in an amount from 0.01 to 50 wt %, preferably from 0.01 to 20 wt % and particularly rom 0.1 to 15 wt %, can also consists of a mixture of several polymers and can, by addition of other polymers exerting a thickening action, be modified in terms of its hair-setting properties.
According to the invention, by film-forming, hair-setting polymers are meant polymers which when used in a 0.01 to 5% aqueous, alcoholic or aqueous-alcoholic solution are capable of depositing a polymer film onto the hair thus setting the hair.
Suitable synthetic nonionic, film-forming, hair-setting polymers that can be used in the hair-treating agent according to the invention are homopolymers of vinylpyrrolidone, homopolymers of N-vinylformamide, copolymers of vinylpyrrolidone and vinyl acetate, terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides or polyethylene glycols with a molecular weight of 800 to 20,000 g/mole.
The suitable synthetic film-forming anionic polymers include crotonic acid-vinyl acetate copolymers and the terpolymers of acrylic acid, ethyl acrylate and N-tert.butylacrylamide.
Natural film-forming polymers or polymers derived therefrom by chemical modification can also be used in the hair-treating agents according to the invention. Useful in this respect are low-molecular-weight chitosan with a molecular weight of 30,000 to 70,000 g/mole, or high-molecular-weight chitosan, mixtures of oligo- mono- and disaccharides, Chinese gum rosin, cellulose derivatives such as hydroxypropylcellulose with a molecular weight of 30,000 to 50,000 g/mol, or shellac in neutralized or un-neutralized form.
Amphoteric polymers can also be used in the hair-treating agents of the invention. Suitable are, for example, copolymers of octylacrylamide, tert.butylaminoethyl methacrylate and two or more monomers from the group consisting of acrylic acid, methacrylic acid and derivatives thereof.
Suitable cationic polymers that can be used according to the invention are the copolymers of vinylpyrrolidone and the quaternized derivatives of dialkylaminoacrylates and methacrylates, for example vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Other suitable cationic polymers are, for example, the copolymer of vinylpyrrolidone and vinylimidazolium methochloride, the terpolymer of dimethyidiallylammonium chloride, sodium acrylate and acrylamide, the terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam, the quaternized ammonium salt prepared from hydroxyethylcellulose and a trimethylammonium-substituted epoxide, the vinylpyrrolidone-methacrylamidopropyltrimethylammonium chloride copolymer and diquaternary polydimethylsiloxanes.
The consistency of the hair-treating agents according to the invention can be increased by addition of a thickener. Suitable for this purpose are, for example, the homopolymers of acrylic acid having a molecular weight of 2,000,000 to 6,000,000 g/mole. Also suitable are the copolymers of acrylic acid and acrylamide (sodium salt) with a molecular weight of 2,000,000 to 6,000,000 g/mole and sclerotium gum. Copolymers of acrylic acid and methacrylic acid are also suitable.
Usually, other known cosmetic additives can be added to the hair-treating agent according to the invention, for example nonsettting nonionic polymers, such as polyethylene glycol with a molecular weight of about 600 g/mole, nonsetting anionic and natural polymers as well as mixture thereof, in an amount of, preferably, 0.01 to 50 wt %. It is also possible to add perfumes in an amount from 0.01 to 5 wt %, opacifiers such as ethylene glycol distearate in an amount from 0.01 to 5 wt %, wetting agents or emulsifiers belonging to the classes of anionic, cationic, amphoteric or nonionic surfactants, such as fatty alcohol sulfates, ethoxylated fatty alcohols, fatty acid alkanolamides and the esters of hydrogenated castor fatty acids in an amount from 0.1 to 30 wt %, moreover humectants, dyes, light stabilizers, anti-oxidants and preservatives in an amount from 0.01 to 10 wt %.
The hair-treating agents according to the invention can also be improved by addition of conventional silicone polymers, for example polydimethylsiloxane (INCI: dimethicone), xcex1-hydro-xcfx89-hydroxy-polyoxydimethylsilylene (INCI: dimethiconol), cyclic dimethylpolysiloxane (INCI: cyclomethicone), trimethyl(octadecyloxy)silane (INCI: stearoxytrimethylsilane), dimethylsiloxane/glycol copolymer (INCI: dimethicone copolyol), dimethylsiloxane-aminoalkylsiloxane copolymer with hydroxyl end groups (INCI: amodimethicone), monomethylpolysiloxane with lauryl side chains and polyoxyethylene and/or polyoxypropylene terminal blocks (INCI: laurylmethicone copolyol), dimethylsiloxane-glycol copolymer acetate (INCI: dimethicone copolyol acetate) and dimethylsiloxane-aminoalkylsiloxane copolymer with trimethylsilyl end groups (INCI: trimethylsilylamodimethicone). Preferred silicone polymers are dimethicone, cyclomethicone and dimethiconol). Mixtures of silicone polymers are also suitable, for example a mixture of dimethicone and dimethiconol.
The names given in parenthesis are those of the INCI (International Cosmetic Ingredients) nomenclature developed for the naming of cosmetic active and auxiliary ingredients.
The agents according to the invention can be used in different application forms, for example in aerosol preparations, as foams or sprays, or as a non-aerosols which are used by means of a pump or as a xe2x80x9cpump and sprayxe2x80x9d. The use of common oil-in-water [O/W] and water-in-oil [W/O] emulsions is also possible as is the use in application forms such as lotions, milk, liquid fixatives, creams, gels, foaming gels, waxes or microemulsions.
The agents according to the invention can also be formulated as coloring or grooming hair-treating agents, for example as color fixatives and hair rinses.
When the agent of the invention is in the form of an aerosol hair spray or aerosol hair coating, it contains additionally 15 to 85 wt % and preferably 25 to 75 wt % of a propellant and it is packed in a pressurized container. Suitable propellants are, for example, the lower alkanes, for example n-butane, isobutane and propane or mixtures thereof with dimethyl ether, furthermore propellants which at the pressures involved are gaseous, for example N2, N2O and CO2 and mixtures of the aforesaid propellants.
The hair-setting agents of the invention can also be in the form of a non-aerosol hair spray or non-aerosol coating sprayable by means of an appropriate mechanical spraying device. By mechanical spraying devices are meant devices which make it possible to spray a liquid without the use of a propellant. A suitable mechanical spraying device is, for example, a spray pump or an elastic container provided with a spray valve and in which the cosmetic agent of the invention is contained under pressure. This pressure causes the elastic container to expand so that, when the spray valve is opened, the agent is forced out continuously by the contraction of the elastic container.
By hair treatment is meant primarily the treatment of human hair for the purpose of providing a hair-do or for hair-grooming purposes.
The following examples illustrate the object of the invention in greater detail. The described hair fixatives are characterized, in particular, by the fact that they provide long-lasting hair setting. After the first hair washing, the polymer network continues to adhere to the hair which results in lasting hair fixation. Depending on the system chosen, three to five washings may be sufficient to restore the untreated hair condition.